CN106633048A - Polyacetylenic compound and preparation method thereof - Google Patents

Abstract

The invention belongs to the technical field of organic chemistry, and discloses a polyalkyne amine compound and a preparation method thereof. The method comprises the following steps: (1) under the protection of an inert gas, in a catalytic system and an organic solvent, a binary alkyne halide compound and a binary sulfonamide compound are mixed, reacted, and cooled to obtain a reaction mother liquor; (2) The reaction mother liquor is added into a precipitant for precipitation, and the precipitate is collected and dried to a constant weight to obtain a polyalkyne amine compound. The preparation method of the present invention is simple, the reaction is efficient, and the group tolerance is strong, and various functional groups can be introduced into the monomer; the prepared polyalkyne amine compound contains carbon-carbon triple bonds, and is used as an intermediate for further reactions It has important applications; and the compound is easy to hydrolyze, and has great application prospects in environmentally friendly chemistry and green chemistry such as degradable materials.

Description

A kind of polyalkyne amine compound and preparation method thereof

technical field

The invention belongs to the technical field of organic chemistry and relates to the synthesis of polyalkyne amine compounds, in particular to a polyalkyne amine compound and a method for preparing the polyalkyne amine compound by reacting an alkyne halide and a sulfonamide.

Background technique

The development of new polymerization reactions is of great importance to polymer materials science. Alkynes are one of the chemical raw materials that are easy to obtain or synthesize. The use of alkynes to construct functional polymers has important academic and technical significance, and has attracted widespread attention from scientists. The coupling polymerization of alkyne amines has the characteristics of mild reaction conditions, high reaction efficiency, and atom economy. It meets the definition of green chemical reactions and is a new type of polymerization reaction. At present, small molecules based on alkyne amines have been widely reported, and are widely used as intermediates of organic products, organic functional materials and bioactive compounds. The molecule becomes one of the more valuable synthetic intermediates.

However, the coupling polymerization reaction of alkyne amines has not been studied and reported in the organic field. Therefore, it can be predicted that the development of simple and efficient synthesis routes of polyalkyne amines will have important scientific significance and application value.

Contents of the invention

The purpose of the present invention is to provide a preparation method of polyalkyne amine compound, which belongs to the green chemical reaction with simple operation, high reaction efficiency and atom economy.

Another object of the present invention is to provide the polyalkyne amine compound obtained by the above method, which has a triple bond in its structure and will also have important applications as an intermediate for further reactions. At the same time, the compound is easily hydrolyzed and has great potential in the development of environmentally friendly and green chemistry such as degradable materials.

The object of the present invention is achieved through the following technical solutions:

A kind of preparation method of polyalkyne amine compound, comprises the following steps:

(1) under the protection of an inert gas, in a catalytic system and an organic solvent, the binary alkyne halide compound and the binary sulfonamide compound are mixed, reacted, and cooled to obtain a reaction mother liquor;

(2) adding the reaction mother liquor into a precipitating agent for precipitation, collecting the precipitate and drying it to a constant weight to obtain a polyalkyne amine compound.

The molar ratio of the reaction between the binary alkyne halide compound and the binary sulfonamide compound in step (1) is 1:1, and the concentration of the binary alkyne halide compound in the organic solvent is 0.1-0.2 mol/L.

The catalytic system described in step (1) is a system containing CuSO ₄ .5H ₂ O, K ₂ CO ₃ and 1,10-phenanthroline;

The amount of CuSO4·5H ₂ O is 10-20mol% of the amount of binary alkyne halide compound, the amount of 1,10-phenanthroline is 20-40mol% of the amount of binary alkyne halide compound, K ₂ CO ₃ in The concentration in organic solvent is 0.2-0.4mol/L.

The organic solvent is one of dimethylsulfoxide (DMSO) or N,N-dimethylformamide (DMF).

The temperature of the reaction described in step (1) is 50-100°C, and the reaction time is 24-48h;

Precipitating agent is methanol in step (2).

The method of adding the reaction mother liquor to the precipitant in step (2) is dropwise (the speed of dripping is 1 to 3 drops/second), and the reaction mother liquor is diluted with tetrahydrofuran before being added to the precipitant, and then carried out after dilution. filter.

The structural formula of the binary alkyne halide compound described in the step (1) is: Wherein X is a chlorine atom or a bromine atom; R is selected from any of the following 16-26, and is not limited to the following 16-26; wherein R ₁ and R ₂ are the same or different, and R ₁ is an alkylene group (-C _n H _2n -, n is an integer), alkyleneoxy (-C _n H _2n O-, n is an integer), oxygen (O), phenylene, one or more C in the alkylene is substituted by phenyl (the number of substituted carbons is less than the number of carbons in the alkylene group), one or more Cs in the alkyleneoxy group are substituted by phenyl and/or oxygen (the number of substituted carbons is less _than the number of carbons in the alkylene group); One or more of alkyl (-C _n H _2n -, n is an integer), alkyleneoxy (-C _n H _2n O-, n is an integer), oxygen (O), phenylene, and alkylene C is substituted by phenyl (the number of substituted carbons is less than the number of carbons in the alkylene group), one or more Cs in the alkyleneoxy group are substituted by phenyl and/or oxygen (the number of substituted carbons is less than the number of carbons in the alkylene group) ;* is the connection;

The binary sulfonamide compound is selected from any one of the following 1-15, and is not limited to the following 15: wherein R ₁ is an alkylene group (-C _n H _2n -, n is an integer), an alkylene oxide Group (-C _n H _2n O-, n is an integer), oxygen (O), phenylene, and one or more Cs in the alkylene group are substituted by phenyl (the number of carbons substituted is less than the number of carbons in the alkylene group) , one or more C in the alkyleneoxy group is substituted by phenyl and/or oxygen (the carbon number of substitution is less _than the carbon number in the alkylene group); R2 is substituted by alkyl, alkoxy, phenyl, or alkyl Phenyl, phenyl substituted by alkoxy, one or more C in the alkyl is substituted by phenyl (the carbon number of substitution is less than the carbon number in the alkyl), one or more C in the alkoxy is phenyl and/or Or oxygen substitution (the carbon number of the substitution is less than the carbon number in the alkylene group);

The present invention also provides a polyalkyne amine compound prepared by the above method.

The structure of the polyalkyne amine compound is Wherein, R ₁ , R _1′ and R ₂ are the corresponding groups in the original structure after the reaction of the above-mentioned binary alkyne halide compound and binary sulfonamide compound to remove hydrogen halide, and n is an integer between 2-200.

There are still triple bonds in the structure of the polyalkyne amine compound, and it will also have an important application as an intermediate for further reaction. At the same time, the compound is easily hydrolyzed and has great potential in the development of environmentally friendly and green chemistry such as degradable materials.

Compared with prior art, the present invention has following advantage:

1. The present invention uses alkyne halides and sulfonamides to polymerize to obtain polyalkyneamines. As far as we know, this type of polymerization has never been reported, so it has high scientific research value, application value and good development prospects;

2. The preparation method of the present invention has a simple process, and the catalyst and raw materials used are easy to obtain, and can be obtained through purchase or simple experimental operation;

3. The preparation method of the present invention has mild reaction conditions, high efficiency, energy saving, and no by-product formation, and has the characteristics of atom economy;

4. The preparation method of the present invention has strong group tolerance, and can introduce various functional groups into the monomer;

5. The polyalkyneamine compound obtained by the preparation method of the present invention is easy to be hydrolyzed, and has great application prospects in environment-friendly chemistry and green chemistry such as degradable materials.

Description of drawings

Fig. 1 is the polyalkyne amine compound (P1) and its corresponding monomer (M1, M2) and model compound prepared in the example 1 of the present invention and the H NMR spectrum comparison diagram in deuterated DMSO;

Fig. 2 is the comparison chart of carbon nuclear magnetic resonance spectra of the polyalkyne amine compound (P1) and its corresponding monomers (M1, M2) and model compounds prepared in Example 1 of the present invention in deuterated DMSO;

Fig. 3 is the infrared absorption spectrogram of polyalkyne amine compound (P1) and its corresponding monomer (M1, M2) and model compound prepared in Example 1 of the present invention;

Fig. 4 is the fluorescence emission spectrum of the polyalkyne amine compound P2 prepared in Example 4 of the present invention under different water contents;

Fig. 5 is a graph of the quantum yield of the polyalkyne amine compound P2 prepared in Example 4 of the present invention under different water contents.

detailed description

The present invention will be specifically described below in conjunction with the embodiments and drawings, but the protection scope of the present invention is not limited to the following embodiments.

Example 1

A kind of polyalkyne amine compound P1, its structural formula is as follows:

The polyalkyne amine compound is prepared by reacting an alkyne halide with a sulfonamide monomer, and its specific reaction equation is as formula (1):

(1) The synthesis method of monomer M1 is as follows: at 0°C, add 9.0mmol (3.29g) of sulfonyl chloride into a 250mL _two -necked bottle, and then add 150mL of dichloromethane and 36.9mmol (4.03mL) of benzyl Amine, the reaction system was stirred at room temperature for 2 hours, extracted three times with dichloromethane and water, spin-dried, the crude product was separated and purified by silica gel chromatography and dried in vacuum at 40°C to obtain 7.7mmol (3.90g) Product (monomer M1), the productive rate is 85%; 8.20 of M1 monomer in the NMR figure of Fig. 1 is-NH peak, 4.04 is-CH ₂ peak, wherein, 3.32 is water peak, 2.50 is DMSO-d6 peak; Monomer M1 in Fig. 3 has -NH peak;

(2) The synthesis method of monomer M2 is as follows: add 10.0mmol (1.26g) 1,4-diethynylbenzene, 22.0mmol (3.89g) NBS, 2.0mmol (0.34g) silver nitrate in a 250mL single-necked bottle, and then After adding 100mL of acetone, the system was stirred at room temperature for 3 hours, then filtered and spin-dried, the crude product was separated and purified by silica gel chromatography, and after vacuum drying at 40°C, 7.8mmol (2.20g) of the product (monomer M2), productive rate is 78%; The 7.48 place of M2 monomer in the NMR figure of Fig. 1 is the H peak on the benzene ring, wherein, 3.32 is the water peak, and 2.50 is the DMSO-d6 peak; There is carbon three in Fig. 3 bond peak;

(3) The preparation step of the polyalkyne amine compound is: add 0.2mmol (0.11g) monomer M1, 0.2mmol (0.06g) monomer M2, 0.03mmol (0.005g) CuSO in a 10mL polymerization tube ₄ · 5H ₂ O, 0.06mmol (0.01g), 1,10-phenanthroline, 0.6mmol (0.08g) K ₂ CO ₃ , after vacuuming and changing N ₂ , add 2mL DMSO, heat the system to 65°C Stir at a rate of 400 rpm for 24 hours; after the reaction, dilute the reaction system with 2 mL of tetrahydrofuran, filter the system to remove copper sulfate, add it dropwise to the precipitant anhydrous methanol for sedimentation, let stand for 12 hours, filter, and vacuum dry Vacuum drying at a temperature of 40°C yielded 0.12g of polymer P1 with a yield of 86% and a molecular weight of 18000g/mol; as can be seen from the P1 map in the NMR image of Figure 1, the -NH peak of the monomer M1 has disappeared. And _-CH2 shifts from 4.04 to 4.65, wherein, 3.32 is the water peak, 2.50 is the DMSO-d6 peak; the disappearance of -NH in P1 after the observable reaction in Figure 3, the existence of the carbon-carbon triple bond peak;

(4) The specific reaction equation of the model compound is as follows:

The preparation steps of the model compound are as follows: add 2.0mmol (0.57g) substrate 1, 4.2mmol (1.10g) substrate 2, 0.4mmol (0.10g) CuSO ₄ 5H ₂ O, 0.8 mmol (0.14), 1,10-phenanthroline, 8.0mmol (1.11g) K ₂ CO ₃ , after vacuuming and changing N ₂ , add 10mL DMSO, heat the system to 65°C and stir at 400 rpm After 36 hours, after the reaction was completed, it was extracted three times with dichloromethane and water, and spin-dried. The crude product was separated and purified by silica gel chromatography and dried in vacuum at 40° C. to obtain 1.8 mmol (1.16 g) of product with a yield of 90%. .

The polyalkyne amine compound (P1) prepared in this embodiment and its corresponding monomer (M1, M2) and the model compound are shown in Figure 1 in deuterated DMSO, and in deuterated DMSO, the NMR spectrum is shown in Figure 1. As shown in Figure 2, the infrared absorption spectrum is shown in Figure 3.

Example 2

In this example, the reaction time in Example 1 was changed to 80° C., and other preparation conditions were the same as in Example 1 to obtain 0.13 g of polymer with a yield of 90% and a molecular weight of 17000 g/mol.

Example 3

In this example, the feeding of CuSO ₄ 5H ₂ O in Example 1 was changed to 0.04mmol (0.007g), the feeding of 1,10-phenanthroline was changed to 0.08mmol (0.02g), and the feeding of K ₂ CO ₃ was changed to 0.80mmol (0.11g), and other preparation conditions were the same as the preparation method of Example 1 to obtain 0.12g of polymer with a yield of 81% and a molecular weight of 18000g/mol.

Example 4

A kind of polyalkyne amine compound P2, shown in its structural formula:

The polyalkyne amine compound is prepared by reacting an alkyne halide with a sulfonamide monomer, and its specific reaction equation is as formula (2):

(1) The synthetic method of monomer M1 is described in Example 1;

(2) The synthesis method of monomer M3 is as follows: 3.0mmol (1.14g) of diethynyltetraphenylethylene, 6.6mmol (1.17g) of NBS, 0.6mmol (0.10g) of silver nitrate were added to a 250mL single-necked bottle, After adding 60mL of acetone, the system was stirred at room temperature for 3 hours, then filtered and spin-dried, the crude product was separated and purified by silica gel chromatography, and 2.7mmol (1.45g) of the product was obtained after vacuum drying at 40°C. The yield was 90%;

Diethynyltetraphenylethylene in this step is according to literature [Hu, R.; Lam, J.W.Y.; Liu, J.; Sung, H.H.Y.; Williams, I.D.; Yue, Z.; Wong, K.S.; , B.Z., Hyperbranchedconjugated poly(tetraphenylethene):synthesis, aggregation-induced emission, fluorescent photopatterning, optical limiting and explosive detection. Polymer Chemistry 2012,3(6),1481-1489.]Preparation method disclosed;

(3) The preparation steps of the polyalkyne amine compounds are as follows: 0.2mmol (0.10g) of monomer M1, 0.2mmol (0.11g) of monomer M3, 0.03mmol (0.005g) of CuSO were sequentially added to a 10mL polymerization tube ₄ · 5H ₂ O, 0.06mmol (0.01g), 1,10-phenanthroline, 0.6mmol (0.08g) K ₂ CO ₃ , after vacuuming and changing N ₂ , add 2mL DMSO, heat the system to 65°C Stir at a rate of 400 rpm for 24 hours; after the reaction, dilute the reaction system with 2 mL of tetrahydrofuran, filter the system to remove copper sulfate, add it dropwise to the precipitant anhydrous methanol for sedimentation, let stand for 12 hours, filter, and vacuum dry Vacuum drying at a temperature of 40° C. yielded 0.15 g of polymer P2 with a yield of 86% and a molecular weight of 11,000 g/mol.

The polymer obtained by this method has special photoelectric properties, and Fig. 4 shows the fluorescence emission spectra of the polymer P2 at different water contents. As the water content increases, the luminescence of the polymer solution gradually increases, and when the water content is 95%, the polymer has the highest luminescence efficiency in the solution. Fig. 5 is a diagram of the quantum yield of polymer P2 at different water contents (excitation wavelength is 340nm), when the water content is 95%, the highest quantum yield is 24.7%.

Example 5

A kind of polyalkyne amine compound P3, shown in its structural formula:

The polyalkyne amine compound is prepared by reacting an alkyne halide with a sulfonamide monomer, and its specific reaction equation is as formula (3):

(1) The synthesis method of monomer M4 is as follows: at 0°C, add 9.0mmol (3.29g) sulfonyl chloride to a 250mL _two -necked bottle, and then add 150mL dichloromethane and 36.9mmol (2.05mL) ethyl Amine, the reaction system was stirred at room temperature for 2 hours, extracted three times with dichloromethane and water, spin-dried, the crude product was separated and purified by silica gel chromatography and dried in vacuum at 40°C to obtain 8.1mmol (3.11g) Product (monomer M4), the yield is 90%;

(2) The synthetic method of monomer M5 is:

(2-1) Add 15.0mmol (3.43g) of bisphenol A, 45mmol (6.22g) of potassium carbonate and 33.0mmol (8.25g) of p-bromobenzyl bromide into a 250mL two-necked bottle, then add 100mL of acetone to the reaction system, and heat to reflux After reacting for 12 hours, cool down, wash the white precipitate repeatedly with deionized water, and obtain 7.64 g of white solid product 1 after drying, with a yield of 90%;

(2-2) Add 10.0mmol (5.66g) white solid 1, 0.5mmol (0.35g) bistriphenylphosphine palladium dichloride, 0.5mmol (0.10g) cuprous iodide, 0.5mmol (0.13g) triphenylphosphine, and vacuumize three times with nitrogen gas, then add 100mL triethylamine and 20mL redistilled tetrahydrofuran to the reaction system, then add 4mL (30.0mmol) triphenylphosphine into the system Methylsilylacetylene, heated to 90°C for 24 hours, cooled, quenched with 100mL saturated ammonium chloride solution, filtered, the filtrate was extracted three times with dichloromethane, the organic phases were combined and concentrated, and the obtained crude product was chromatographed on silica gel The column was separated, and the eluent was petroleum ether, and 5.40 g of white solid product 2 was obtained, and the yield was 90%;

(2-3) Add 5.0mmol (3.00g) of white solid 2 and 25.0mmol (1.40g) of potassium hydroxide into a 250mL single-necked bottle, then add 25mL of methanol, 25mL of tetrahydrofuran, and 5mL of deionized water, and stir at room temperature for 12 After 1 hour, the reaction mixture was extracted three times with dichloromethane, the organic phases were combined and concentrated, and the obtained crude product was separated by silica gel chromatography, and the eluent was petroleum ether to obtain 2.17 g of white solid product 3 with a yield of 95%. ;

(2-4) Add 2.5mmol (1.14g) of white solid 3, 5.5mmol (0.98g) of NBS, 0.5mmol (0.08g) of silver nitrate into a 250mL single-necked bottle, and then add 60mL of acetone, then stir the system at room temperature After 3 hours, it was filtered and spin-dried, and the crude product was separated and purified by silica gel chromatography, and dried in vacuum at 40°C to obtain 1.38 g of the product, namely monomer M5, with a yield of 90%;

(3) The preparation step of the polyalkyne amine compound is: add 0.2mmol (0.08g) monomer M4, 0.2mmol (0.12g) monomer M5, 0.03mmol (0.005g) CuSO in a 10mL polymerization tube ₄ · 5H ₂ O, 0.06mmol (0.01g), 1,10-phenanthroline, 0.6mmol (0.08g) K ₂ CO ₃ , after vacuuming and changing N ₂ , add 2mL DMSO, heat the system to 65°C Stir at a rate of 400 rpm for 24 hours; after the reaction, dilute the reaction system with 2 mL of tetrahydrofuran, filter the system to remove copper sulfate, add it dropwise to the precipitant anhydrous methanol for sedimentation, let stand for 12 hours, filter, and store at 40°C 0.13 g of polymer P3 was obtained after drying under vacuum at 100°C with a yield of 78%.

The above-mentioned embodiments of the present invention are only examples for clearly illustrating the present invention, rather than limiting the implementation of the present invention. For those of ordinary skill in the art, on the basis of the above description, other changes or changes in different forms can also be made. It is not necessary and impossible to exhaustively list all the implementation manners here. All modifications, equivalent replacements and improvements made within the spirit and principles of the present invention shall be included within the protection scope of the claims of the present invention.

Claims (10)

1. a preparation method of polyalkyne amine compound, is characterized in that: comprise the following steps: (1) under the protection of an inert gas, in a catalytic system and an organic solvent, the binary alkyne halide compound and the binary sulfonamide compound are mixed, reacted, and cooled to obtain a reaction mother liquor; (2) adding the reaction mother liquor into a precipitating agent for precipitation, collecting the precipitate and drying it to a constant weight to obtain a polyalkyne amine compound. 2. according to the preparation method of the described polyalkyne amine compound of claim 1, it is characterized in that: The structural formula of the binary alkyne halide compound described in the step (1) is: Wherein X is a chlorine atom or a bromine atom; R is selected from any one of the following 16-26, and is not limited to the following 16-26; wherein R ₁ and R ₂ are the same or different, and R ₁ is an alkylene group that is -C _n H _2n -, alkyleneoxy is -C _n H _2n O-, oxygen, phenylene, one or more C in alkylene is substituted by phenyl, one or more C in alkylene is substituted by benzene and/or substituted by oxygen; R ₂ is alkylene, that is -C _n H _2n -, alkyleneoxy, that is -C _n H _2n O-, oxygen, phenylene, one or more C in alkylene is replaced by Phenyl substitution, one or more Cs in alkyleneoxy are substituted by phenyl and/or oxygen; * is the link; The binary sulfonamide compound is selected from any one of the following 1-15, and is not limited to the following 15: wherein R ₁ is an alkylene group that is -C _n H _2n -, an alkylene group that is -C _n H _2n O-, oxygen, phenylene, one or more C in alkylene is substituted by phenyl, one or more C in alkyleneoxy is substituted by phenyl and/or oxygen _; R2 is alkyl, Alkoxy, phenyl, phenyl substituted by alkyl, phenyl substituted by alkoxy, one or more C in alkyl is substituted by phenyl, one or more C in alkoxy is substituted by phenyl and/or Oxygen substitution; 3. according to the preparation method of the described polyalkyne amine compound of claim 1, it is characterized in that: the mol ratio of binary alkyne halide compound and binary sulfonamide compound reaction described in step (1) is 1:1, binary alkyne The concentration of the halogen compound in the organic solvent is 0.1-0.2mol/L. 4. according to the preparation method of the described polyalkyne amine compound of claim 1, it is characterized in that: the catalytic system described in step (1) is to contain CuSO ₄ 5H ₂ O, K ₂ CO ₃ and 1,10-phenanthro phylloline system. 5. according to the preparation method of the described polyalkyne amine compound of claim 4, it is characterized in that: the consumption of described CuSO 5H ₂ O is the 10-20mol% of binary alkyne halide compound consumption, 1,10-phenanthroline The dosage is 20-40mol% of that of the binary alkyne halide compound, and the concentration of K ₂ CO ₃ in the organic solvent is 0.2-0.4mol/L. 6. The preparation method of the polyalkyne amine compound according to claim 1, characterized in that: the organic solvent is one of dimethylsulfoxide or N,N-dimethylformamide. 7. The preparation method of the polyalkyne amine compound according to claim 1, characterized in that: the reaction temperature in step (1) is 50-100°C, and the reaction time is 24-48h. 8. according to the preparation method of the described polyalkyne amine compound of claim 1, it is characterized in that: the precipitation agent described in step (2) is methyl alcohol. 9. according to the preparation method of the described polyalkyne amine compound of claim 1, it is characterized in that: the mode that reaction mother liquor is added in the precipitating agent described in step (2) is dripping, and before reaction mother liquor is added in the precipitating agent, use THF was diluted and filtered after dilution. 10. A polyalkyneamine compound obtained by the preparation method according to any one of claims 1 to 9.